1. Field of the Invention
This invention relates to liquid hydroxyurethane products of bis-carbonates of bis-glycidyl ethers and to a process for their preparation. More particularly, this invention relates to liquid hydroxyurethanes having cyclocarbonate end groups products prepared by reacting a molar excess of a bis-carbonate of a bis-glycidyl ether with a difunctional diamine such as a polyoxypropylenediamine.
Bis-carbonates of bis-glycidyl ethers, which are materials known in the art, have been suggested for use in preparing urethane materials, polyurethane polyols, polyester polyurethane polyols, polyether polyurethane polyols, polycarbonate polyurethane polyols and as additives for curing agent formulations such as those utilized for curing of epoxy resins. Because some of these bis-carbonates of bis-glycidyl ethers are solid-liquid mixtures, i.e., i.e., two phase materials, they are not satisfactory for mixing with the usual liquid formulations employed, for example, in the curing of epoxy resins. The bis-carbonates prepared from the bis-glycidyl ether of 1,4-cyclohexanedimethanol and from the bis-glycidyl ether of neopentyl glycol are mainly solid at room temperature and at 60.degree. C. the bis-carbonate of the bis-glycidyl ether of 1,4-cyclohexanedimethanol is about one-half solid and one-half liquid while the bis-carbonate of the bis-glycidyl ether of neopentyl glycol is about three-quarters liquid and about one-quarter solid.
The invention of this application relates to the reaction of a molar excess of these liquid-solid materials with a polyoxypropylenediamine to yield hydroxyurethane products which contain active carbonate groups and which are single phase, single layered, viscous liquids at room temperature. Thus, by the process of this invention these bis-carbonates surprisingly are converted from troublesome, liquid-solid materials to viscous liquids containing no solids which are generally clear, single phase, single layered liquids.
2. Prior Art
U.S. Pat. No. 5,175,231 to Rappoport et al., teaches a method for preparing a urethane by reacting a compound containing a plurality of cyclocarbonate groups with a diamine in which the two amine groups have different reactivities with cyclocarbonate so as to form a urethane oligomer with amine end groups. The urethane oligomer can then be reacted in different ways to form a polyurethane.
United Kingdom Patent No. 1,495,555 to Petrov et al. (December, 1977), discloses a method for producing a polyurethane by reacting a hydrocarbon polymer having at least one double bond such as cis-1,4-polyisoprene, polybutadiene, etc. with a primary or secondary amine, such as benzylamine, xylylene diamine, etc. These products which have a wide range of uses, e.g., shoes, tires, adhesives and coatings, have good strength, elasticity, abrasion resistance, dynamic properties, resistance to low temperatures and bond strongly to metals.
U.S.S.R. Inventor's Certificate No. 359,255 to Petrov et al. (Jan. 11, 1973), discloses the preparation of polyurethanes by the reaction of oligomer diamines such as oligomer diamine diurethane formed by reacting polyoxypropylene dicarbonate with xylenediamine and then in a second step reacting oligomer diamine with tricyclocarbonate based on trimethylolpropane triglycidyl ether to form a cross-linked urethane elastomer.
U.S.S.R. Inventor's Certificate No. 351,835 to Shapiro et al. (Oct. 19, 1972), teaches a process for preparing polyesters suitable for use in the synthesis of polyurethanes by reaction of a diglycidyl compound, such as ethylene glycol diglycidyl ether and carbon dioxide in the presence of a tetraalkylammonium halide.
U.S.S.R. Inventor's Certificate No. 413,824A to Petrov et al. (Dec. 24, 1969), discloses a process for preparing polymer materials with a urethane group in the chain by reaction of an epoxy resin with a polyamine containing urethane groups which are obtained by the reaction of a primary or secondary diamine with bicyclic carbonates.
U.S. Pat. No. 2,802,022 to Grozos discloses a process for preparing polyurethanes in which a hydroxy carbonate formed by reacting a cyclic carbonate with, for example, a polyamine and in a second step reacting the hydroxyl carbonate with urea to form the corresponding polyurethane.
U.S. Pat. No. 3,072,613 to Whelan, Jr., et al., teaches the preparation of resinous polyurethane products by the reaction of a multiple cyclic carbonate and polyfunctional aliphatic amines having a plurality of reactive amine groups. These polymeric substances are readily cast into tough, colorless films having excellent clarity and tear resistance by extrusion or solvent casting techniques.
U.S. Pat. No. 2,935,494 to Whelan, Jr. teaches a process for the preparation of polymeric compositions from erythritol dicarbonate and polyfunctional aliphatic amines having a plurality of reactive amine groups such as unhindered primary aliphatic diamines as exemplified by ethylene diamine, hexamethylene diamine, etc.